JP7280822B2 - laminated glass - Google Patents

Description

TECHNICAL FIELD The present invention relates to an interlayer film for laminated glass having an infrared reflective layer. The present invention also relates to laminated glass using the interlayer film for laminated glass.

Laminated glass generally scatters a small amount of glass fragments even if it is broken by an external impact, and is excellent in safety. Therefore, the laminated glass is widely used in automobiles, railroad vehicles, aircraft, ships, buildings, and the like. The laminated glass is manufactured by sandwiching an interlayer film for laminated glass between a pair of glass plates. Laminated glass used for openings of such vehicles and buildings is required to have high heat shielding properties.

In some cases, an intermediate film having an infrared reflective layer is used to improve heat shielding properties. An intermediate film having an infrared reflective layer is disclosed in Patent Document 1 below.

In addition, laminated glass may be required to have good design and design. Colorless laminated glass as well as colored laminated glass are known. A colored interlayer film used to obtain colored laminated glass is disclosed in Patent Document 2 below. This intermediate film contains a coloring agent.

JP 2017-81775 A JP 2010-248026 A

For example, laminated glass with interlayers is installed in vehicle openings. Sunlight is incident on the laminated glass attached to the opening of the vehicle, and the laminated glass is exposed to high temperatures.

Laminated glass using a conventional colored interlayer may be discolored by light and heat. As a result, the design and design of the laminated glass may be impaired.

SUMMARY OF THE INVENTION An object of the present invention is to provide an interlayer film for laminated glass that is capable of suppressing discoloration due to light and heat in an interlayer film having a resin layer colored with a coloring agent. Another object of the present invention is to provide a laminated glass using the interlayer film for laminated glass.

According to a broad aspect of the present invention, it has an infrared reflective layer and a first resin layer containing a thermoplastic resin, and the first resin layer is disposed on the first surface side of the infrared reflective layer. The infrared reflective layer has a first maximum reflection wavelength at a wavelength of 350 nm to 450 nm and a second maximum reflection wavelength at a wavelength of 800 nm or more, and the reflectance at the first maximum reflection wavelength and the second The reflectance at the maximum reflection wavelength of each is 15% or more, and the first resin layer contains a coloring agent (hereinafter sometimes referred to as an intermediate film) for laminated glass. .

On the specific situation with the intermediate film which concerns on this invention, the said infrared reflective layer contains a metal sputtering layer.

In a specific aspect of the interlayer film according to the present invention, the colorant is a perylene compound, phthalocyanine compound, naphthalocyanine compound, or anthracyanine compound.

In a specific aspect of the intermediate film according to the present invention, the first resin layer contains heat shielding particles.

It is preferable that the thermoplastic resin in the first resin layer is a polyvinyl acetal resin.

It is preferable that the first resin layer contains a plasticizer.

In a specific aspect of the intermediate film according to the present invention, the intermediate film includes a second resin layer, and the second resin layer is provided on the second surface side opposite to the first surface of the infrared reflective layer. A resin layer is arranged.

It is preferable that the thermoplastic resin in the second resin layer is a polyvinyl acetal resin.

It is preferable that the second resin layer contains a plasticizer.

According to a broad aspect of the present invention, it comprises a first laminated glass member, a second laminated glass member, and the above-described interlayer film for laminated glass, wherein the interlayer film has a second resin layer, or not, and when the intermediate film has the second resin layer, the second resin layer is arranged on the second surface side opposite to the first surface of the infrared reflective layer When the intermediate film has the second resin layer, the first laminated glass member is arranged outside the first resin layer, and the second laminated glass member is arranged outside the second resin layer. 2 laminated glass members are arranged, and when the intermediate film does not have the second resin layer, the first laminated glass member is arranged outside the first resin layer, A laminated glass is provided, wherein the second laminated glass member is arranged outside an infrared reflective layer.

In a specific aspect of the laminated glass according to the present invention, in a building or a vehicle, the laminated glass is provided in an opening between an exterior space and an interior space into which heat rays are incident from the exterior space. The laminated glass is mounted so that the laminated glass member is positioned on the outer space side and the first laminated glass member is positioned on the inner space side.

An interlayer film for laminated glass according to the present invention has an infrared reflective layer and a first resin layer containing a thermoplastic resin. In the interlayer film for laminated glass according to the present invention, the first resin layer is arranged on the first surface side of the infrared reflective layer. In the interlayer film for laminated glass according to the present invention, the infrared reflective layer has a first maximum reflection wavelength at a wavelength of 350 nm to 450 nm and a second maximum reflection wavelength at a wavelength of 800 nm or more, and the first maximum The reflectance at the reflection wavelength and the second maximum reflection wavelength are each 15% or more. In the interlayer film for laminated glass according to the present invention, the first resin layer contains a colorant. Since the interlayer film for laminated glass according to the present invention has the above configuration, discoloration due to light and heat can be suppressed in the interlayer film including the resin layer colored with the coloring agent.

FIG. 1 is a cross-sectional view schematically showing an interlayer film for laminated glass according to a first embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing an interlayer film for laminated glass according to a second embodiment of the present invention. FIG. 3 is a cross-sectional view schematically showing an example of laminated glass using the interlayer film for laminated glass shown in FIG. FIG. 4 is a cross-sectional view schematically showing an example of laminated glass using the interlayer film for laminated glass shown in FIG.

The present invention will be described in detail below.

(Interlayer film for laminated glass)

An intermediate film for laminated glass according to the present invention (hereinafter sometimes referred to as an intermediate film) has an infrared reflective layer and a first resin layer containing a thermoplastic resin. In the intermediate film according to the present invention, the first resin layer is arranged on the first surface side of the infrared reflective layer. In the intermediate film according to the present invention, the infrared reflective layer has a first maximum reflection wavelength at a wavelength of 350 nm to 450 nm and a second maximum reflection wavelength at a wavelength of 800 nm or more, and at the first maximum reflection wavelength The reflectance and the reflectance at the second maximum reflection wavelength are each 15% or more. In the intermediate film according to the present invention, the first resin layer contains a colorant.

Since the intermediate film according to the present invention has the above configuration, discoloration due to light and heat can be suppressed in the intermediate film including the resin layer colored with the coloring agent. The laminated glass using the interlayer film according to the present invention, for example, in a building or a vehicle, has the first resin layer in the opening between the exterior space and the interior space where heat rays are incident from the exterior space. It can be attached so as to be located on the inner space side. In this case, heat rays such as sunlight are sufficiently reflected by the infrared reflecting layer before reaching the first resin layer. Heat rays such as sunlight generally include rays with wavelengths of 350 nm to 450 nm and rays with wavelengths of 800 nm or longer. In the present invention, since the reflectance of both the first maximum reflection wavelength of 350 nm to 450 nm and the second maximum reflection wavelength of 800 nm or more is increased, discoloration due to light can be suppressed, and heat is applied. It is also possible to suppress discoloration due to

The intermediate film may have a maximum absorption wavelength of less than 350 nm, which is different from the first and second maximum absorption wavelengths. The intermediate film may have a maximum absorption wavelength of 350 nm to 450 nm different from the first maximum absorption wavelength, and the reflectance of the maximum absorption wavelength may be less than 15%. The intermediate film may have a maximum absorption wavelength of more than 450 nm and less than 800 nm, different from the first and second maximum absorption wavelengths. The intermediate film may have a maximum absorption wavelength of 800 nm or more, which is different from the second maximum absorption wavelength, and the reflectance of the maximum absorption wavelength may be less than 15%.

The maximum absorption wavelength of the infrared reflective layer is measured as follows.

In accordance with JIS R3106:1998, the reflectance is measured using a spectrophotometer ("U-4100" manufactured by Hitachi High-Tech Co., Ltd.), and the wavelength showing the maximum value of the resulting spectrum is defined as the maximum absorption wavelength.

The first resin layer contains a colorant. Therefore, the visible light transmittance of the intermediate film may be low. From the viewpoint of further enhancing visibility through laminated glass, the visible light transmittance of the intermediate film is preferably 20% or higher, more preferably 50% or higher, and even more preferably 70% or higher. From the viewpoint of further enhancing the appearance and design of the laminated glass, the visible light transmittance of the intermediate film is preferably 88% or less, more preferably 87% or less, and even more preferably 86% or less.

The visible light transmittance is measured at a wavelength of 380 nm to 780 nm in accordance with JIS R3211:1998 using a spectrophotometer ("U-4100" manufactured by Hitachi High-Tech Co., Ltd.).

The intermediate film may or may not have a second resin layer. From the viewpoint of further enhancing the adhesiveness between the laminated glass member and the intermediate film, the intermediate film may have a second resin layer. When the said intermediate film has a said 2nd resin layer, a said 2nd resin layer is arrange|positioned at the 2nd surface side opposite to the said 1st surface of the said infrared reflection layer.

The intermediate film may be wound into a roll to form an intermediate film roll. The roll body may include a winding core and an intermediate film. The intermediate film may be wound around the outer periphery of the winding core.

Hereinafter, specific embodiments of the present invention will be described with reference to the drawings.

FIG. 1 is a cross-sectional view schematically showing an interlayer film for laminated glass according to a first embodiment of the present invention.

The intermediate film 11 shown in FIG. 1 is a multilayer intermediate film having a structure of three or more layers. The intermediate film 11 is used to obtain laminated glass. The intermediate film 11 is an intermediate film for laminated glass. The intermediate film 11 includes an infrared reflective layer 1 , a first resin layer 2 and a second resin layer 3 . A first resin layer 2 is arranged and laminated on the first surface 1a side of the infrared reflective layer 1 . A second resin layer 3 is arranged and laminated on the side of the second surface 1b opposite to the first surface 1a of the infrared reflective layer 1 . The infrared reflective layer 1 is an intermediate layer. The first resin layer 2 and the second resin layer 3 are protective layers, respectively, and are surface layers in this embodiment. The infrared reflecting layer 1 is arranged and sandwiched between the first resin layer 2 and the second resin layer 3 . Therefore, the intermediate film 11 has a multilayer structure in which the first resin layer 2, the infrared reflective layer 1, and the second resin layer 3 are laminated in this order (first resin layer 2/infrared reflective layer 1/second resin layer 2). of resin layer 3).

FIG. 2 is a cross-sectional view schematically showing an interlayer film for laminated glass according to a second embodiment of the present invention.

The intermediate film 11A shown in FIG. 2 is a multilayer intermediate film having a two-layer structure. The intermediate film 11A is used to obtain laminated glass. The intermediate film 11A is an intermediate film for laminated glass. 11 A of intermediate films are equipped with the infrared reflection layer 1 and the 1st resin layer 2. As shown in FIG. A first resin layer 2 is arranged and laminated on the first surface 1a side of the infrared reflective layer 1 . The intermediate film 11A has a multilayer structure (first resin layer 2/infrared reflecting layer 1) in which the first resin layer 2 and the infrared reflecting layer 1 are laminated in this order.

Other layers may be arranged between the first resin layer 2 and the infrared reflective layer 1 and between the infrared reflective layer 1 and the second resin layer 3, respectively. Preferably, the first resin layer 2 and the infrared reflecting layer 1, and the infrared reflecting layer 1 and the second resin layer 3 are directly laminated. Other layers include adhesive layers, layers comprising polyethylene terephthalate, and the like.

Other details of each member constituting the interlayer film and the laminated glass according to the present invention will be described below.

(Infrared reflective layer)

The infrared reflective layer reflects infrared rays. The infrared reflective layer has a first maximum reflection wavelength of 350 nm to 450 nm and a second maximum reflection wavelength of 800 nm or more. The reflectances at the first maximum reflection wavelength and the second maximum reflection wavelength are respectively 15% or more. An infrared reflective layer having such properties is selected and used.

From the viewpoint of effectively suppressing discoloration due to light and heat, the infrared reflective layer preferably includes a metal sputtering layer. The metal sputtering layer can be formed by metal sputtering. The infrared reflective layer including the metal sputtering layer may be a resin film with a metal foil.

Examples of the infrared reflective layer include a resin film with metal foil, a multilayer laminate film in which a metal layer and a dielectric layer are formed on a resin layer, a film containing graphite, a multilayer resin film, a liquid crystal film, and the like. These films have the ability to reflect infrared radiation.

The infrared reflective layer is preferably a resin film with metal foil, a film containing graphite, a multilayer resin film, or a liquid crystal film. These films have fairly good infrared reflective performance. Therefore, by using these films, it is possible to obtain a laminated glass which has a higher heat shielding property and can maintain a high visible light transmittance for a longer period of time.

The resin film with metal foil includes a resin film and a metal foil laminated on the outer surface of the resin film. Materials for the resin film include polyethylene terephthalate resin, polyethylene naphthalate resin, polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic acid copolymer resin, polyurethane resin, polyvinyl alcohol resin, polyolefin resin, poly Examples include vinyl chloride resins and polyimide resins. Materials for the metal foil include aluminum, copper, silver, gold, palladium, and alloys containing these.

The multilayer laminate film in which a metal layer and a dielectric layer are formed on a resin layer is a multilayer laminate film in which metal layers and dielectric layers are alternately laminated on a resin layer (resin film) in an arbitrary number of layers. In the multilayer laminated film in which the metal layer and the dielectric layer are formed on the resin layer, it is preferable that all the metal layers and the dielectric layers are alternately laminated. There may be a structural portion that is not alternately laminated, such as layer/metal layer/metal layer/dielectric layer/metal layer.

Materials for the resin layer (resin film) in the multilayer laminated film include the same materials as those for the resin film in the metal foil-attached resin film. Materials for the resin layer (resin film) in the multilayer laminated film include polyethylene, polypropylene, polylactic acid, poly(4-methylpentene-1), polyvinylidene fluoride, cyclic polyolefin, polymethyl methacrylate, polyvinyl chloride, and polyvinyl. alcohol, polyamides such as nylon 6, 11, 12, 66, polystyrene, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, polyester, polyphenylene sulfide and polyetherimide. Examples of the material of the metal layer in the multilayer laminated film include the same materials as the material of the metal foil in the resin film with metal foil. Both or one side of the metal layer can be provided with a coating layer of a metal or a mixed oxide of metals. Materials for the coating layer include ZnO _{, Al2O3} , _Ga2O3 , _InO3 , _MgO , Ti, NiCr and Cu.

Examples of the material for the dielectric layer in the multilayer laminated film include indium oxide.

The multilayer resin film is a laminated film in which a plurality of resin films are laminated. Examples of the material for the multilayer resin film include materials similar to those for the resin layer (resin film) in the multilayer laminated film. The number of laminated resin films in the multilayer resin film is 2 or more, may be 3 or more, or may be 5 or more. The number of laminated resin films in the multilayer resin film may be 1000 or less, 100 or less, or 50 or less.

The multilayer resin film may be a multilayer resin film in which two or more thermoplastic resin layers having different optical properties (refractive indices) are alternately or randomly laminated in an arbitrary number of layers. Such a multilayer resin film is constructed so as to obtain desired infrared reflective performance.

Examples of the liquid crystal film include a film obtained by laminating an arbitrary number of cholesteric liquid crystal layers that reflect light of an arbitrary wavelength. Such a liquid crystal film is constructed so as to obtain desired infrared reflective performance.

The infrared reflective layer preferably has an infrared transmittance of 40% or less in at least one wavelength within the range of 800 nm to 2000 nm because it has excellent infrared reflective performance. The infrared transmittance of the infrared reflective layer used in the examples described later satisfies the above preferable conditions. At least one wavelength within the range of 800 nm to 2000 nm, the infrared transmittance is more preferably 30% or less, more preferably 20% or less.

Specifically, the transmittance of each wavelength in the wavelength range of 800 nm to 2000 nm of the infrared reflective layer is measured as follows. A single infrared reflective layer is provided. Using a spectrophotometer ("U-4100" manufactured by Hitachi High-Tech Co., Ltd.), the spectral transmittance of the infrared reflective layer at wavelengths of 800 nm to 2000 nm is obtained in accordance with JIS R3106:1998 or JIS R3107:2013. In accordance with JIS R3107:2013, it is preferable to obtain the spectral transmittance of each wavelength of the infrared reflective layer from 800 nm to 2000 nm.

(First resin layer and second resin layer)

Thermoplastic resin:

The first resin layer contains a thermoplastic resin (hereinafter sometimes referred to as thermoplastic resin (1)). The first resin layer preferably contains a polyvinyl acetal resin (hereinafter sometimes referred to as polyvinyl acetal resin (1)) as the thermoplastic resin (1). The second resin layer contains a thermoplastic resin (hereinafter sometimes referred to as thermoplastic resin (2)), and the thermoplastic resin (2) is polyvinyl acetal resin (hereinafter referred to as polyvinyl acetal resin (2)). may be described).

The thermoplastic resin (1) and the thermoplastic resin (2) may be the same or different. Each of the thermoplastic resin (1) and the thermoplastic resin (2) may be used alone or in combination of two or more. Each of the polyvinyl acetal resin (1) and the polyvinyl acetal resin (2) may be used alone, or two or more thereof may be used in combination.

Examples of the thermoplastic resin include polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic acid copolymer resin, polyurethane resin, polyvinyl alcohol resin, polyolefin resin, polyvinyl acetate resin, polystyrene resin and ionomer resin. is mentioned. Thermoplastic resins other than these may be used.

The thermoplastic resin is preferably a polyvinyl acetal resin. Combined use of the polyvinyl acetal resin and the plasticizer further increases the adhesion of the resin layer to other layers such as the laminated glass member and the infrared reflective layer.

The polyvinyl acetal resin can be produced, for example, by acetalizing polyvinyl alcohol (PVA) with an aldehyde. The polyvinyl acetal resin is preferably an acetalized product of polyvinyl alcohol. The polyvinyl alcohol is obtained, for example, by saponifying polyvinyl acetate. The degree of saponification of the polyvinyl alcohol is generally in the range of 70-99.9 mol %.

The average degree of polymerization of the polyvinyl alcohol (PVA) is preferably 200 or more, more preferably 500 or more, still more preferably 1500 or more, still more preferably 1600 or more, particularly preferably 2600 or more, most preferably 2700 or more, preferably It is 5,000 or less, more preferably 4,000 or less, and still more preferably 3,500 or less. When the average degree of polymerization is at least the lower limit, the penetration resistance of the laminated glass is further enhanced. Molding of a resin layer becomes it easy that the said average degree of polymerization is below the said upper limit.

The average degree of polymerization of polyvinyl alcohol is determined by a method based on JIS K6726 "Polyvinyl alcohol test method".

The number of carbon atoms in the acetal group contained in the polyvinyl acetal resin is not particularly limited. Aldehyde used when producing the polyvinyl acetal resin is not particularly limited. The acetal group in the polyvinyl acetal resin preferably has 3 to 5 carbon atoms, more preferably 3 or 4 carbon atoms. When the number of carbon atoms in the acetal group in the polyvinyl acetal resin is 3 or more, the glass transition temperature of the resin layer becomes sufficiently low.

The aldehyde is not particularly limited. Generally, aldehydes having 1 to 10 carbon atoms are preferably used. Examples of the aldehyde having 1 to 10 carbon atoms include propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, and n-nonylaldehyde. , n-decylaldehyde, formaldehyde, acetaldehyde and benzaldehyde. Propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexylaldehyde or n-valeraldehyde are preferred, propionaldehyde, n-butyraldehyde or isobutyraldehyde are more preferred, and n-butyraldehyde is even more preferred. Only one kind of the aldehyde may be used, or two or more kinds thereof may be used in combination.

The hydroxyl content (hydroxy group content) of the polyvinyl acetal resin is preferably 15 mol% or more, more preferably 18 mol% or more, still more preferably 20 mol% or more, particularly preferably 28 mol% or more, preferably 40 mol%. % or less, more preferably 35 mol % or less, still more preferably 32 mol % or less. When the hydroxyl content is equal to or higher than the lower limit, the adhesive strength of the resin layer is further increased. Further, when the content of the hydroxyl group is equal to or less than the upper limit, the flexibility of the resin layer is increased, and the handling of the resin layer is facilitated.

The content of hydroxyl groups in the polyvinyl acetal resin is the molar fraction obtained by dividing the amount of ethylene groups to which hydroxyl groups are bonded by the total amount of ethylene groups in the main chain, expressed as a percentage. The amount of ethylene groups to which the hydroxyl groups are bonded can be measured according to, for example, JIS K6728 "Polyvinyl butyral test method".

The degree of acetylation (acetyl group content) of the polyvinyl acetal resin is preferably 0.1 mol% or more, more preferably 0.3 mol% or more, still more preferably 0.5 mol% or more, and preferably 30 mol% or less. , more preferably 25 mol % or less, still more preferably 20 mol % or less, particularly preferably 15 mol % or less, and most preferably 3 mol % or less. Compatibility of polyvinyl acetal resin and a plasticizer becomes it high that the said degree of acetylation is more than the said minimum. When the degree of acetylation is equal to or less than the upper limit, the laminated glass has high humidity resistance.

The degree of acetylation is the molar fraction obtained by dividing the amount of ethylene groups to which acetyl groups are bonded by the total amount of ethylene groups in the main chain, expressed as a percentage. The amount of ethylene groups to which the acetyl groups are bonded can be measured according to, for example, JIS K6728 "Polyvinyl butyral test method".

The degree of acetalization of the polyvinyl acetal resin (degree of butyralization in the case of polyvinyl butyral resin) is preferably 60 mol% or more, more preferably 63 mol% or more, preferably 85 mol% or less, more preferably 75 mol%. 70 mol % or less, more preferably 70 mol % or less. Compatibility of polyvinyl acetal resin and a plasticizer becomes it high that the said degree of acetalization is more than the said minimum. When the degree of acetalization is equal to or less than the upper limit, the reaction time required for producing the polyvinyl acetal resin is shortened.

The degree of acetalization is determined as follows. First, a value is obtained by subtracting the amount of ethylene groups to which hydroxyl groups are bonded and the amount of ethylene groups to which acetyl groups are bonded from the total amount of ethylene groups in the main chain. The obtained value is divided by the total amount of ethylene groups in the main chain to obtain the mole fraction. The degree of acetalization is the value of this mole fraction expressed as a percentage.

The hydroxyl content (hydroxyl group amount), the degree of acetalization (degree of butyralization) and the degree of acetylation are preferably calculated from the results of measurements according to JIS K6728 "Polyvinyl butyral test method". However, measurement according to ASTM D1396-92 may be used. When the polyvinyl acetal resin is a polyvinyl butyral resin, the hydroxyl content (hydroxyl group amount), the degree of acetalization (degree of butyralization), and the degree of acetylation are determined according to JIS K6728 "Polyvinyl butyral test method". can be calculated from the results measured by

Plasticizer:

From the viewpoint of further increasing the adhesive strength of the resin layer, the first resin layer preferably contains a plasticizer. From the viewpoint of further increasing the adhesive strength of the resin layer, the second resin layer preferably contains a plasticizer. When the thermoplastic resin contained in the resin layer is a polyvinyl acetal resin, it is particularly preferred that the resin layer contain a plasticizer. The layer containing polyvinyl acetal resin preferably contains a plasticizer.

The plasticizer is not particularly limited. Conventionally known plasticizers can be used as the plasticizer. Only one type of the plasticizer may be used, or two or more types may be used in combination.

Examples of the plasticizer include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, and organic phosphoric acid plasticizers such as organic phosphoric acid plasticizers and organic phosphorous acid plasticizers. . Organic ester plasticizers are preferred. Preferably, the plasticizer is a liquid plasticizer.

Examples of the monobasic organic acid esters include glycol esters obtained by reacting a glycol with a monobasic organic acid. Examples of the glycol include triethylene glycol, tetraethylene glycol and tripropylene glycol. Examples of the monobasic organic acids include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid, n-octylic acid, 2-ethylhexylic acid, n-nonylic acid and decylic acid.

Examples of the polybasic organic acid esters include ester compounds of polybasic organic acids and alcohols having a linear or branched structure having 4 to 8 carbon atoms. Examples of the polybasic organic acids include adipic acid, sebacic acid and azelaic acid.

Examples of the organic ester plasticizer include triethylene glycol di-2-ethylpropanoate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol di-n-octanoate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethylbutyrate, 1,3-propylene glycol di-2-ethylbutyrate, 1,4-butylene glycol di-2-ethylbutyrate, diethylene glycol di-2-ethylbutyrate, diethylene glycol di-2-ethylhexanoate, dipropylene glycol Di-2-ethylbutyrate, triethylene glycol di-2-ethylpentanoate, tetraethylene glycol di-2-ethylbutyrate, diethylene glycol dicaprylate, dihexyl adipate, dioctyl adipate, hexyl cyclohexyl adipate, adipine Mixtures of heptyl acid and nonyl adipate, diisononyl adipate, diisodecyl adipate, heptyl nonyl adipate, dibutyl sebacate, oil-modified alkyd sebacate, mixtures of phosphate and adipate, and the like. Organic ester plasticizers other than these may be used. Other adipic acid esters than those mentioned above may be used.

Examples of the organic phosphoric acid plasticizer include tributoxyethyl phosphate, isodecylphenyl phosphate and triisopropyl phosphate.

The plasticizer is preferably a diester plasticizer represented by the following formula (1).

In the above formula (1), R1 and R2 each represent an organic group having 5 to 10 carbon atoms, R3 represents an ethylene group, an isopropylene group or an n-propylene group, and p represents an integer of 3 to 10. . Each of R1 and R2 in the above formula (1) is preferably an organic group having 6 to 10 carbon atoms.

The plasticizer preferably contains triethylene glycol di-2-ethylhexanoate (3GO) or triethylene glycol di-2-ethylbutyrate (3GH), and triethylene glycol di-2-ethylhexanoate more preferably.

The content of the plasticizer is not particularly limited. In the layer containing the plasticizer (first resin layer or second resin layer), the content of the plasticizer is preferably 25 parts by weight or more, more preferably 100 parts by weight of the thermoplastic resin. is 30 parts by weight or more, more preferably 35 parts by weight or more. In the layer containing the plasticizer (first resin layer or second resin layer), the content of the plasticizer is preferably 75 parts by weight or less, more preferably 100 parts by weight of the thermoplastic resin. is 60 parts by weight or less, more preferably 50 parts by weight or less, particularly preferably 40 parts by weight or less. When the content of the plasticizer is at least the lower limit, the penetration resistance of the laminated glass is further enhanced. When the content of the plasticizer is equal to or less than the upper limit, the transparency of the laminated glass is further enhanced.

Colorant:

The first resin layer contains a colorant. The second resin layer may contain a coloring agent. The content of the colorant in the second resin layer may be less than the content of the colorant in the first resin layer. In addition, when the first resin layer has a shade region containing a colorant, the first resin layer preferably contains a colorant in a region other than the shade region. Only one kind of the coloring agent may be used, or two or more kinds thereof may be used in combination.

Examples of the coloring agent include pigments and dyes.

Pigments and dyes are distinguished as follows.

A polyvinyl butyral resin (using n-butyraldehyde, polymerization degree of polyvinyl alcohol: 1700, hydroxyl group content: 30 mol%, acetylation degree: 1 mol%, butyralization degree: 69 mol%) is prepared. 0.015% by weight per 100% by weight of the total amount of 100 parts by weight of this polyvinyl butyral resin, 40 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO), and the polyvinyl butyral resin, 3GO, and colorant A kneaded product is obtained by kneading with a coloring agent in an amount corresponding to 1 part. This kneaded product is extruded to obtain a resin film having a thickness of 760 μm. This resin film is placed between two sheets of clear glass (thickness: 2.5 mm) having a visible light transmittance of 90% measured according to JIS R3106:1998 to produce a laminated glass. A coloring agent with which the obtained laminated glass has a haze value of 0.35% or more is defined as a pigment. A colorant that results in a haze value of less than 0.35% is defined as a dye.

The pigment may be an organic pigment or an inorganic pigment. The organic pigment may be an organic pigment having a metal atom, or may be an organic pigment having no metal atom. Only one type of the pigment may be used, or two or more types may be used in combination.

Examples of the organic pigments include phthalocyanine compounds, quinacdrine compounds, azo compounds, pentaphene compounds, dioxazine compounds, perylene compounds, indole compounds and dioxazine compounds.

Examples of the inorganic pigments include carbon black, iron oxide, zinc oxide, and titanium oxide.

The coloring agent is preferably a phthalocyanine compound, a naphthalocyanine compound, an anthracyanine compound, a quinacdrine compound, an azo compound, a pentaphene compound, a dioxazine compound, a perylene compound, an indole compound, or carbon black.

From the viewpoint of effectively enhancing designability and designability and effectively suppressing discoloration due to light and heat, the coloring agent is at least one of a perylene compound, a phthalocyanine compound, a naphthalocyanine compound and an anthracyanine compound. is preferably component X-1 of From the viewpoint of more effectively enhancing designability and designability and more effectively suppressing discoloration due to light and heat, the coloring agent is at least one of a phthalocyanine compound, a naphthalocyanine compound and an anthracyanine compound. It is more preferred to be component X of the seed.

The above component X is not particularly limited. As component X, conventionally known phthalocyanine compounds, naphthalocyanine compounds and anthracyanine compounds can be used.

Examples of the component X include phthalocyanine, phthalocyanine derivatives, naphthalocyanine, naphthalocyanine derivatives, anthracyanine, and anthracyanine derivatives. Each of the phthalocyanine compound and the phthalocyanine derivative preferably has a phthalocyanine skeleton. Each of the naphthalocyanine compound and the naphthalocyanine derivative preferably has a naphthalocyanine skeleton. Each of the anthracyanine compound and the anthracyanine derivative preferably has an anthracyanine skeleton.

From the viewpoint of further increasing the heat shielding property, the component X is preferably phthalocyanine, a phthalocyanine derivative, naphthalocyanine or a naphthalocyanine derivative, more preferably phthalocyanine or a phthalocyanine derivative.

From the viewpoint of effectively increasing the heat shielding property and maintaining the visible light transmittance at a higher level for a long period of time, the component X preferably contains vanadium atoms or copper atoms. The component X preferably contains vanadium atoms, and also preferably contains copper atoms. Component X is more preferably at least one of phthalocyanines containing vanadium atoms or copper atoms and derivatives of phthalocyanines containing vanadium atoms or copper atoms. From the viewpoint of further suppressing multiple images of the laminated glass and further increasing the heat shielding property, the component X preferably has a structural unit in which an oxygen atom is bonded to a vanadium atom.

From the viewpoint of further enhancing designability, it is preferable that the content of the colorant and the content of component X-1 and component X satisfy the following preferred ranges.

The content of the coloring agent in 100% by weight of the layer containing the coloring agent (first resin layer or second resin layer) is preferably 0.001% by weight or more, more preferably 0.002% by weight. Above, more preferably 0.003% by weight or more, particularly preferably 0.004% by weight or more, and most preferably 0.005% by weight or more. The content of the coloring agent in 100% by weight of the layer (first resin layer or second resin layer) containing the coloring agent is preferably 10% by weight or less, more preferably 9% by weight or less, and even more preferably is 8% by weight or less, particularly preferably 7% by weight or less. When the content of the coloring agent is at least the lower limit, the designability and designability are further improved. When the content of the coloring agent is equal to or less than the upper limit, the visibility through the laminated glass is further enhanced.

The content of the colorant is preferably 0.001% by weight or more, more preferably 0.001% by weight or more, in 100% by weight of the region excluding the shade region of the layer containing the colorant (first resin layer or second resin layer). is 0.002% by weight or more, more preferably 0.003% by weight or more, particularly preferably 0.004% by weight or more, and most preferably 0.005% by weight or more. The content of the coloring agent is preferably 10% by weight or less, more preferably 9% by weight, in 100% by weight of the region excluding the shaded region of the layer containing the coloring agent (first resin layer or second resin layer). % by weight or less, more preferably 8% by weight or less, particularly preferably 7% by weight or less. When the content of the coloring agent is at least the lower limit, the designability and designability are further enhanced. When the content of the coloring agent is equal to or less than the upper limit, the visibility through the laminated glass is further enhanced.

The content of the component X-1 and the component X in 100% by weight of the layer (the first resin layer or the second resin layer) containing the component X-1 and the component X is preferably 0.5%. 001% by weight or more, more preferably 0.002% by weight or more, still more preferably 0.003% by weight or more, particularly preferably 0.004% by weight or more, and most preferably 0.005% by weight or more. The content of the component X-1 and the component X in 100% by weight of the layer (the first resin layer or the second resin layer) containing the component X-1 and the component X is preferably 10% by weight. Below, more preferably 9% by weight or less, still more preferably 8% by weight or less, and particularly preferably 7% by weight or less. When the contents of component X-1 and component X are equal to or higher than the above lower limits, designability and designability are further enhanced. When the content of the coloring agent is equal to or less than the upper limit, the visibility through the laminated glass is further enhanced.

The content of the component X-1 and the component X in 100% by weight of the region excluding the shade region of the layer (first resin layer or second resin layer) containing the component X-1 and the component X is , preferably 0.001% by weight or more, more preferably 0.002% by weight or more, and still more preferably 0.003% by weight or more. The content of the component X-1 and the component X in 100% by weight of the region excluding the shade region of the layer (first resin layer or second resin layer) containing the component X-1 and the component X is , particularly preferably 0.004% by weight or more, most preferably 0.005% by weight or more. The content of the component X-1 and the component X in 100% by weight of the region excluding the shade region of the layer (first resin layer or second resin layer) containing the component X-1 and the component X is , preferably 10% by weight or less, more preferably 9% by weight or less, still more preferably 8% by weight or less, and particularly preferably 7% by weight or less. When the contents of component X-1 and component X are equal to or higher than the above lower limits, designability and designability are further enhanced. When the content of the coloring agent is equal to or less than the upper limit, the visibility through the laminated glass is further enhanced.

Thermal insulation material:

The first resin layer preferably contains a heat shielding substance. The content of the heat insulating substance in the second resin layer may be less than the content of the heat insulating substance in the first resin layer. The second resin layer preferably contains a heat shielding substance. The second resin layer may not contain a heat shielding substance. Only one type of the above heat shielding substance may be used, or two or more types may be used in combination.

Preferably, the heat shielding material contains at least one component X selected from phthalocyanine compounds, naphthalocyanine compounds and anthracyanine compounds, or heat shielding particles. In this case, both the component X and the heat-shielding particles may be included.

The first resin layer preferably contains at least one component X selected from phthalocyanine compounds, naphthalocyanine compounds and anthracyanine compounds. The content of the component X in the second resin layer may be less than the content of the component X in the first resin layer. The second resin layer preferably contains the component X. The second resin layer may not contain the component X. As for the component X, only one type may be used, or two or more types may be used in combination.

The above component X also corresponds to a heat shielding substance. From the viewpoint of effectively improving the heat shielding property, the first resin layer preferably contains the component X. The content of the component X in the second resin layer may be less than the content of the component X in the first resin layer. From the viewpoint of effectively improving the heat shielding property, the second resin layer preferably contains the component X. The second resin layer may not contain the component X. As for the component X, only one type may be used, or two or more types may be used in combination.

From the viewpoint of effectively enhancing heat shielding properties, the content of component X preferably satisfies the following preferred range.

The content of the component X in 100% by weight of the layer (first resin layer or second resin layer) containing the component X is preferably 0.001% by weight or more, more preferably 0.005% by weight. Above, more preferably 0.01% by weight or more, particularly preferably 0.02% by weight or more. The content of the component X in 100% by weight of the layer (first resin layer or second resin layer) containing the component X is preferably 0.2% by weight or less, more preferably 0.1% by weight. Below, more preferably 0.05% by weight or less, particularly preferably 0.04% by weight or less. When the content of component X is equal to or more than the lower limit and equal to or less than the upper limit, the heat shielding property is sufficiently high, and the visible light transmittance is sufficiently high. For example, it is possible to increase the visible light transmittance to 70% or more.

The first resin layer preferably contains heat shielding particles. The content of the heat shielding particles in the second resin layer may be less than the content of the heat shielding particles in the first resin layer. The second resin layer preferably contains the heat shielding particles. The second resin layer may not contain heat shielding particles. The heat-shielding particles are a heat-shielding substance. Infrared rays (heat rays) can be effectively blocked by using heat shielding particles. Only one type of the heat-shielding particles may be used, or two or more types may be used in combination.

From the viewpoint of further enhancing the heat shielding properties of the laminated glass, the heat shielding particles are more preferably metal oxide particles. The heat-shielding particles are preferably particles (metal oxide particles) formed of a metal oxide.

Infrared rays with a wavelength of 780 nm or longer, which is longer than visible light, have a smaller amount of energy than ultraviolet rays. However, infrared rays have a large thermal effect, and when infrared rays are absorbed by substances, they are released as heat. For this reason, infrared rays are generally called heat rays. By using the heat-shielding particles, infrared rays (heat rays) can be effectively blocked. The heat-shielding particles mean particles capable of absorbing infrared rays.

Specific examples of the heat shielding particles include aluminum-doped tin oxide particles, indium-doped tin oxide particles, antimony-doped tin oxide particles (ATO particles), gallium-doped zinc oxide particles (GZO particles), and indium-doped zinc oxide particles (IZO particles). ), aluminum-doped zinc oxide particles (AZO particles), niobium-doped titanium oxide particles, sodium-doped tungsten oxide particles, cesium-doped tungsten oxide particles, thallium-doped tungsten oxide particles, rubidium-doped tungsten oxide particles, tin-doped indium oxide particles (ITO particles) , tin-doped zinc oxide particles and silicon-doped zinc oxide particles, and lanthanum hexaboride (LaB ₆ ) particles. Heat shielding particles other than these may be used. Metal oxide particles are preferred because they have a high heat ray shielding function, ATO particles, GZO particles, IZO particles, ITO particles or tungsten oxide particles are more preferred, and ITO particles or tungsten oxide particles are particularly preferred. In particular, tin-doped indium oxide particles (ITO particles) are preferred, and tungsten oxide particles are also preferred, since they have a high heat ray shielding function and are easily available.

From the viewpoint of further enhancing the heat shielding properties of the laminated glass, the tungsten oxide particles are preferably metal-doped tungsten oxide particles. The above "tungsten oxide particles" include metal-doped tungsten oxide particles. Specific examples of the metal-doped tungsten oxide particles include sodium-doped tungsten oxide particles, cesium-doped tungsten oxide particles, thallium-doped tungsten oxide particles, and rubidium-doped tungsten oxide particles.

Cesium-doped tungsten oxide particles are particularly preferred from the viewpoint of further increasing the heat shielding properties of the laminated glass. From the viewpoint of further enhancing the heat shielding properties of the laminated glass, the cesium-doped tungsten oxide particles are preferably tungsten oxide particles represented by the formula: Cs _0.33 WO ₃ .

The average particle size of the heat-shielding particles is preferably 0.01 μm or more, more preferably 0.02 μm or more, preferably 0.1 μm or less, and more preferably 0.05 μm or less. If the average particle size is at least the above lower limit, the heat ray shielding property will be sufficiently high. When the average particle size is equal to or less than the above upper limit, the dispersibility of the heat shielding particles is enhanced.

The above "average particle size" indicates the volume average particle size. The average particle size can be measured using a particle size distribution analyzer (“UPA-EX150” manufactured by Nikkiso Co., Ltd.) or the like.

The content of the heat shielding particles in 100% by weight of the layer (first resin layer or second resin layer) containing the heat shielding particles is preferably 0.01% by weight or more, more preferably 0.1% by weight. % by weight or more, more preferably 1% by weight or more, particularly preferably 1.5% by weight or more. The content of the heat shielding particles in 100% by weight of the layer containing the heat shielding particles (the first resin layer or the second resin layer) is preferably 6% by weight or less, more preferably 5.5% by weight. 4% by weight or less, particularly preferably 3.5% by weight or less, and most preferably 3% by weight or less. When the content of the heat-shielding particles is at least the lower limit and not more than the upper limit, the heat-shielding properties are sufficiently high, and the visible light transmittance is sufficiently high.

Metal salt:

The first resin layer preferably contains a metal salt that is an alkali metal salt, an alkaline earth metal salt, or a magnesium salt (hereinafter sometimes referred to as metal salt M). The second resin layer preferably contains the metal salt M described above. The use of the metal salt M makes it easy to control the adhesiveness between the resin layer and the infrared reflective layer and the laminated glass member. Only one kind of the metal salt M may be used, or two or more kinds thereof may be used in combination.

The metal salt M preferably contains a metal Li, Na, K, Rb, Cs, Mg, Ca, Sr or Ba. The metal salt contained in the resin layer preferably contains K or Mg.

The metal salt M is an alkali metal salt of an organic acid having 2 to 16 carbon atoms, an alkaline earth metal salt of an organic acid having 2 to 16 carbon atoms, or a magnesium salt of an organic acid having 2 to 16 carbon atoms. is more preferred, and a magnesium salt of a carboxylic acid having 2 to 16 carbon atoms or a potassium salt of a carboxylic acid having 2 to 16 carbon atoms is more preferred.

Examples of the magnesium salt of a carboxylic acid having 2 to 16 carbon atoms and the potassium salt of a carboxylic acid having 2 to 16 carbon atoms include magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, magnesium 2-ethylbutyrate, and 2-ethylbutanoic acid. potassium, magnesium 2-ethylhexanoate and potassium 2-ethylhexanoate;

The total content of Mg and K in the layer containing the metal salt M (first resin layer or second resin layer) is preferably 5 ppm or more, more preferably 10 ppm or more, still more preferably 20 ppm or more, preferably is 300 ppm or less, more preferably 250 ppm or less, still more preferably 200 ppm or less. When the total content of Mg and K is the above lower limit or more and the above upper limit or less, the adhesion between the resin layer and the infrared reflective layer and the laminated glass member can be controlled even better.

UV shielding agent:

The first resin layer preferably contains an ultraviolet shielding agent. The second resin layer preferably contains an ultraviolet shielding agent. The use of the ultraviolet shielding agent makes it more difficult for the visible light transmittance to decrease even when the laminated glass is used for a long period of time. Only one type of the ultraviolet shielding agent may be used, or two or more types may be used in combination.

The ultraviolet shielding agent includes an ultraviolet absorber. The ultraviolet shielding agent is preferably an ultraviolet absorber.

Examples of the ultraviolet shielding agent include an ultraviolet shielding agent containing a metal atom, an ultraviolet shielding agent containing a metal oxide, an ultraviolet shielding agent having a benzotriazole structure (benzotriazole compound), and an ultraviolet shielding agent having a benzophenone structure (benzophenone compound ), an ultraviolet shielding agent having a triazine structure (triazine compound), an ultraviolet shielding agent having a malonic ester structure (malonic acid ester compound), an ultraviolet shielding agent having an oxalic acid anilide structure (oxalic acid anilide compound) and a benzoate structure UV shielding agents (benzoate compounds) and the like can be mentioned.

Examples of the ultraviolet shielding agent containing the metal atom include platinum particles, particles obtained by coating the surfaces of platinum particles with silica, palladium particles, and particles obtained by coating the surfaces of palladium particles with silica. It is preferred that the UV shielding agent is not heat shielding particles.

The ultraviolet shielding agent is preferably an ultraviolet shielding agent having a benzotriazole structure, an ultraviolet shielding agent having a benzophenone structure, an ultraviolet shielding agent having a triazine structure, or an ultraviolet shielding agent having a benzoate structure. The ultraviolet shielding agent is more preferably an ultraviolet shielding agent having a benzotriazole structure or an ultraviolet shielding agent having a benzophenone structure, and more preferably an ultraviolet shielding agent having a benzotriazole structure.

Examples of the ultraviolet shielding agent containing the metal oxide include zinc oxide, titanium oxide and cerium oxide. Furthermore, the surface of the ultraviolet shielding agent containing the metal oxide may be coated. Examples of coating materials for the surface of the ultraviolet shielding agent containing the metal oxide include insulating metal oxides, hydrolyzable organosilicon compounds and silicone compounds.

Examples of the insulating metal oxide include silica, alumina and zirconia. The insulating metal oxide has a bandgap energy of, for example, 5.0 eV or more.

Examples of the ultraviolet shielding agent having the benzotriazole structure include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole ("TinuvinP" manufactured by BASF), 2-(2'-hydroxy-3', 5'-di-t-butylphenyl)benzotriazole (BASF "Tinuvin320"), 2-(2'-hydroxy-3'-t-butyl-5-methylphenyl)-5-chlorobenzotriazole (BASF "Tinuvin 326" manufactured by BASF), and 2-(2'-hydroxy-3',5'-di-amylphenyl)benzotriazole ("Tinuvin 328" manufactured by BASF). The ultraviolet shielding agent is preferably an ultraviolet shielding agent having a benzotriazole structure containing a halogen atom because it has excellent ultraviolet shielding performance, and is preferably an ultraviolet shielding agent having a benzotriazole structure containing a chlorine atom. more preferred.

Examples of the ultraviolet shielding agent having the benzophenone structure include octabenzone (“Chimassorb 81” manufactured by BASF).

Examples of the ultraviolet shielding agent having the triazine structure include "LA-F70" manufactured by ADEKA and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl) oxy]-phenol (“Tinuvin 1577FF” manufactured by BASF) and the like.

Examples of the ultraviolet shielding agent having a malonic acid ester structure include dimethyl 2-(p-methoxybenzylidene)malonate, tetraethyl-2,2-(1,4-phenylenedimethylidene)bismalonate, and 2-(p-methoxybenzylidene). -bis(1,2,2,6,6-pentamethyl-4-piperidinyl)malonate and the like.

Commercially available UV shielding agents having a malonic acid ester structure include Hostavin B-CAP, Hostavin PR-25 and Hostavin PR-31 (all manufactured by Clariant).

Examples of the ultraviolet shielding agent having the oxalic acid anilide structure include N-(2-ethylphenyl)-N'-(2-ethoxy-5-t-butylphenyl)oxalic acid diamide, N-(2-ethylphenyl)- N'-(2-ethoxy-phenyl) oxalic acid diamide, 2-ethyl-2'-ethoxy-oxalanilide ("SanduvorVSU" manufactured by Clariant) and other oxalic acids having an aryl group substituted on the nitrogen atom Diamides are mentioned.

Examples of the ultraviolet shielding agent having a benzoate structure include 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate ("Tinuvin 120" manufactured by BASF). .

The content of the ultraviolet shielding agent in 100% by weight of the layer (first resin layer or second resin layer) containing the ultraviolet shielding agent is preferably 0.1% by weight or more, more preferably 0.2% by weight. % by weight or more, more preferably 0.3% by weight or more, and particularly preferably 0.5% by weight or more. The content of the ultraviolet shielding agent in 100% by weight of the layer (first resin layer or second resin layer) containing the ultraviolet shielding agent is preferably 2.5% by weight or less, more preferably 2% by weight. Below, more preferably 1% by weight or less, particularly preferably 0.8% by weight or less. When the content of the ultraviolet shielding agent is at least the lower limit and not more than the upper limit, the decrease in visible light transmittance after the period has elapsed is further suppressed. In particular, when the content of the ultraviolet shielding agent is 0.2% by weight or more in 100% by weight of the layer containing the ultraviolet shielding agent, the decrease in the visible light transmittance of the laminated glass after the lapse of time is remarkably suppressed. can.

Antioxidant:

The first resin layer preferably contains an antioxidant. The second resin layer preferably contains an antioxidant. Only one kind of the antioxidant may be used, or two or more kinds thereof may be used in combination.

Examples of the antioxidant include phenol antioxidants, sulfur antioxidants, phosphorus antioxidants, and the like. The phenol-based antioxidant is an antioxidant having a phenol skeleton. The sulfur-based antioxidant is an antioxidant containing a sulfur atom. The phosphorus antioxidant is an antioxidant containing a phosphorus atom.

The antioxidant is preferably a phenolic antioxidant or a phosphorus antioxidant.

Examples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol (BHT), butylhydroxyanisole (BHA), 2,6-di-t-butyl-4-ethylphenol, stearyl- β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2′-methylenebis-(4-methyl-6-butylphenol), 2,2′-methylenebis-(4-ethyl-6 -t-butylphenol), 4,4′-butylidene-bis-(3-methyl-6-t-butylphenol), 1,1,3-tris-(2-methyl-hydroxy-5-t-butylphenyl)butane , tetrakis[methylene-3-(3′,5′-butyl-4-hydroxyphenyl)propionate]methane, 1,3,3-tris-(2-methyl-4-hydroxy-5-t-butylphenol)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, bis(3,3'-t-butylphenol)butyric acid glycol ester and bis(3-t-butyl-4-hydroxy-5-methylbenzenepropanoic acid)ethylenebis(oxyethylene). One or more of these antioxidants are preferably used.

Examples of the phosphorus antioxidant include tridecyl phosphite, tris(tridecyl) phosphite, triphenyl phosphite, trinonylphenyl phosphite, bis(tridecyl) pentaerythritol diphosphite, bis(decyl) pentaerythritol diphosphite. Phyto, tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butyl-6-methylphenyl)ethyl ester phosphorous acid, and 2,2′-methylenebis(4 ,6-di-t-butyl-1-phenyloxy)(2-ethylhexyloxy) phosphorous and the like. One or more of these antioxidants are preferably used.

Examples of commercially available antioxidants include "IRGANOX 245" manufactured by BASF, "IRGAFOS 168" manufactured by BASF, "IRGAFOS 38" manufactured by BASF, "Sumilizer BHT" manufactured by Sumitomo Chemical Co., Ltd., manufactured by Sakai Chemical Industry Co., Ltd. "H-BHT", and "IRGANOX 1010" manufactured by BASF.

In order to maintain high visible light transmittance of laminated glass for a long period of time, the antioxidant is contained in 100% by weight of the layer containing the antioxidant (first resin layer or second resin layer). Preferably the amount is at least 0.1% by weight. Moreover, the content of the antioxidant is preferably 2% by weight or less in 100% by weight of the layer containing the antioxidant.

Other Ingredients:

Each of the first resin layer and the second resin layer may optionally have a coupling agent, a dispersant, a surfactant, a flame retardant, an antistatic agent, a pigment, a dye, and an adhesive force adjustment other than a metal salt. Additives such as agents, anti-moisture agents, optical brighteners and infrared absorbers may also be included. Only one of these additives may be used, or two or more thereof may be used in combination.

(Other details of interlayer film for laminated glass)

The thickness of the intermediate film is not particularly limited. From the viewpoint of practical use and the viewpoint of sufficiently enhancing the penetration resistance and bending rigidity of laminated glass, the thickness of the interlayer film is preferably 0.1 mm or more, more preferably 0.25 mm or more, and preferably 3 mm or less. It is preferably 1.5 mm or less. When the thickness of the intermediate film is at least the above lower limit, the penetration resistance and bending rigidity of the laminated glass are further enhanced. When the thickness of the intermediate film is equal to or less than the above upper limit, the transparency of the intermediate film is further improved.

The intermediate film may be an intermediate film having a uniform thickness, or may be an intermediate film having a varying thickness. The cross-sectional shape of the intermediate film may be rectangular or wedge-shaped.

It is preferable that the intermediate film has an uneven shape on its outer surface. In this case, the intermediate film should have an uneven shape on at least one of the outer surfaces on both sides. It is preferable that at least one of the outer surfaces on both sides of the intermediate film has an uneven surface. More preferably, the intermediate film has an uneven shape on both outer surfaces. The outer surface of the intermediate film is preferably embossed. In this case, at least one of the outer surfaces on both sides should be embossed. At least one of the outer surfaces on both sides of the intermediate film is preferably embossed. More preferably, both outer surfaces of the intermediate film are embossed. The method for forming the uneven shape is not particularly limited, and examples thereof include a lip embossing method, an embossing roll method, a calender roll method, and a profile extrusion method. The embossing roll method is preferred because it can form a large number of embossed patterns that are quantitatively constant.

(Laminated glass)

FIG. 3 is a cross-sectional view schematically showing an example of laminated glass using the interlayer film for laminated glass shown in FIG.

A laminated glass 31 shown in FIG. 3 includes a first laminated glass member 21 , a second laminated glass member 22 , and an intermediate film 11 . The intermediate film 11 is arranged and sandwiched between the first laminated glass member 21 and the second laminated glass member 22 .

A first laminated glass member 21 is laminated on the first surface 11 a of the intermediate film 11 . A second laminated glass member 22 is laminated on the second surface 11b of the intermediate film 11 opposite to the first surface 11a. A first laminated glass member 21 is arranged and laminated on the outer surface 2a of the first resin layer 2 . A second laminated glass member 22 is arranged and laminated on the outer surface 3a of the second resin layer 3 .

FIG. 4 is a cross-sectional view schematically showing an example of laminated glass using the interlayer film for laminated glass shown in FIG.

A laminated glass 31A shown in FIG. 4 includes a first laminated glass member 21, a second laminated glass member 22, and an intermediate film 11A. The intermediate film 11A is arranged and sandwiched between the first laminated glass member 21 and the second laminated glass member 22 .

A first laminated glass member 21 is laminated on the first surface 11a of the intermediate film 11A. A second laminated glass member 22 is laminated on a second surface 11b opposite to the first surface 11a of the intermediate film 11A. A first laminated glass member 21 is arranged and laminated on the outer surface 2a of the first resin layer 2 . A second laminated glass member 22 is arranged and laminated on the second surface 1b (outer surface) of the infrared reflective layer 1 .

As described above, the laminated glass according to the present invention includes the first laminated glass member, the second laminated glass member, and the interlayer film, and the interlayer film is the interlayer film for laminated glass according to the present invention. is. In the laminated glass according to the present invention, the intermediate film is arranged between the first laminated glass member and the second laminated glass member. When the intermediate film has the second resin layer, the first laminated glass member is arranged outside the first resin layer, and the second laminated glass member is arranged outside the second resin layer. A laminated glass member is arranged. When the intermediate film does not have the second resin layer, the first laminated glass member is arranged outside the first resin layer, and the second laminated glass member is arranged outside the infrared reflective layer. A glass member is placed.

The laminated glass is arranged in a vehicle such that the first laminated glass member is positioned on the side of the external space in an opening between an external space and an internal space into which heat rays are incident from the external space, and It is preferable that the second laminated glass member is attached so as to be positioned on the inner space side.

The first laminated glass member is preferably the first glass plate. The second laminated glass member is preferably a second glass plate.

Examples of the laminated glass member include a glass plate and a PET (polyethylene terephthalate) film. Laminated glass includes not only laminated glass in which an interlayer film is sandwiched between two glass plates, but also laminated glass in which an interlayer film is sandwiched between a glass plate and a PET film or the like. The laminated glass is a laminate including glass plates, and preferably at least one glass plate is used. The first laminated glass member and the second laminated glass member are glass plates or PET films, respectively, and the laminated glass is one of the first laminated glass member and the second laminated glass member. At least one preferably comprises a glass plate.

Examples of the glass plate include inorganic glass and organic glass. Examples of the inorganic glass include float plate glass, heat-absorbing plate glass, heat-reflecting plate glass, polished plate glass, figured glass, and lined plate glass. The organic glass is a synthetic resin glass that replaces inorganic glass. Examples of the organic glass include a polycarbonate plate and a poly(meth)acrylic resin plate. Examples of the poly(meth)acrylic resin plate include a polymethyl(meth)acrylate plate.

The thickness of the laminated glass member is preferably 1 mm or more, more preferably 1.8 mm or more, still more preferably 2 mm or more, particularly preferably 2.1 mm or more, preferably 5 mm or less, and more preferably 3 mm or less. Further, when the laminated glass member is a glass plate, the thickness of the glass plate is preferably 1 mm or more, more preferably 1.8 mm or more, still more preferably 2 mm or more, particularly preferably 2.1 mm or more, and preferably It is 5 mm or less, more preferably 3 mm or less, still more preferably 2.6 mm or less. When the laminated glass member is a PET film, the thickness of the PET film is preferably 0.03 mm or more and preferably 0.5 mm or less.

It is preferable that each of the first laminated glass member and the second laminated glass member is clear glass or heat-absorbing sheet glass. The second laminated glass member is preferably made of clear glass because it has a high infrared transmittance and further improves the heat shielding property of the laminated glass. The first laminated glass member is preferably a heat-absorbing plate glass because it has a low infrared transmittance and further increases the heat shielding property of the laminated glass. The heat-absorbing plate glass is preferably green glass. Preferably, the second laminated glass member is clear glass, and the first laminated glass member is heat-absorbing plate glass. The heat-absorbing plate glass is a heat-absorbing plate glass conforming to JIS R3208.

The method for producing the laminated glass is not particularly limited. First, an intermediate film is sandwiched between the first laminated glass member and the second laminated glass member to obtain a laminate. Next, for example, the obtained laminated body is passed through a press roll or placed in a rubber bag and vacuum-sucked to form a bond between the first laminated glass member, the second laminated glass member, and the intermediate film. Deaerate any remaining air in between. Thereafter, pre-bonding is performed at about 70-110° C. to obtain a pre-pressed laminate. Next, the pre-pressed laminate is put into an autoclave or pressed and pressed at about 120-150° C. and a pressure of 1-1.5 MPa. Thus, a laminated glass can be obtained. Each layer may be laminated during the production of the laminated glass.

The interlayer film and the laminated glass can be used for automobiles, railway vehicles, aircraft, ships, buildings, and the like. The intermediate film and the laminated glass can be used for purposes other than these uses. The intermediate film and laminated glass are preferably intermediate films and laminated glasses for vehicles or buildings, and more preferably intermediate films and laminated glasses for vehicles. The interlayer film and the laminated glass can be used for automobile windshields, side glasses, rear glasses, roof glasses, and the like. The intermediate film and the laminated glass are suitably used for automobiles. The above interlayer films are used to obtain laminated glass for automobiles. The above-mentioned laminated glass is suitably used for windshields of vehicles. The above-mentioned laminated glass is preferably laminated glass that can be used for windshields of vehicles.

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples. The invention is not limited only to these examples.

(Thermoplastic resin)

Polyvinyl acetal resin (PVB, average polymerization degree 1700, hydroxyl group content 30.5 mol%, acetylation degree 1 mol%, acetalization degree 68.5 mol%)

In the polyvinyl acetal resin used, n-butyraldehyde having 4 carbon atoms is used for acetalization. Regarding the polyvinyl acetal resin, the degree of acetalization (degree of butyralization), the degree of acetylation, and the content of hydroxyl groups were measured according to JIS K6728 "Polyvinyl butyral test method". When measured according to ASTM D1396-92, values similar to those obtained by the method based on JIS K6728 "Polyvinyl butyral test method" were obtained.

(Plasticizer)

Triethylene glycol di-2-ethylhexanoate (3GO)

(coloring agent)

Anthraquinone compound (Component X-1, "Sumiplast Violet RR" manufactured by Sumika Chemtex Co., Ltd.)

Phthalocyanine compound (Component X-1, "NIR-43V" manufactured by Yamada Kagaku Co., Ltd.)

Perylene compound (Component X-1, Clariant "PV Fast Red B")

(Ultraviolet shielding agent)

Tinuvin 326 (2-(2'-hydroxy-3'-t-butyl-5-methylphenyl)-5-chlorobenzotriazole, manufactured by BASF "Tinuvin 326") 0.2 parts by weight

(Antioxidant)

BHT (2,6-di-t-butyl-p-cresol)

The following infrared reflective layer was prepared.

(Infrared reflective layer)

Infrared reflective films 1 to 6 (films with a silver sputtering layer formed on the film, manufactured in-house)

An infrared reflective film 1 was produced according to the following procedure. A polyethylene terephthalate (PET) film (thickness: 50 μm) was used as the base material. Sputtering was performed on the base material using niobium as a target. Sputtering power is medium wave (MF) 1500 W, atmosphere gas is argon gas flow rate of 225 sccm, oxygen gas gas flow rate is 65 sccm, and sputtering pressure is 0.177 Pa. Niobium oxide (Nb ₂ O ₃ ) to form a metal oxide layer having a thickness of 30 nm.

Next, sputtering was performed on the metal oxide layer using niobium as a target. Sputtering power is medium wave (MF) 1500 W, atmosphere gas is argon gas flow rate of 225 sccm and oxygen gas gas flow rate is 30 sccm, pressure during sputtering is 0.170 Pa. ₂ O _x , where x is less than 3) to form an oxygen-deficient metal oxide layer with a thickness of 4 nm.

Then, sputtering was performed on the oxygen-deficient metal oxide layer using silver as a target. Sputtering power was direct current (DC) 1150 W, atmosphere gas was argon, gas flow rate was 225 sccm, and sputtering pressure was 0.28 Pa to form a silver layer with a thickness of 16 nm.

The conditions for sputtering the metal oxide layer, the oxygen-deficient metal oxide layer, and the silver layer were the same as those described above, except that the thickness of each layer to be sputtered was changed. Metal oxide layer (30 nm)/oxygen-deficient metal oxide layer (4 nm)/silver layer (16 nm)/oxygen-deficient metal oxide layer (4 nm)/metal oxide layer (80 nm)/oxygen-deficient metal oxide layer on substrate A conductive layer was formed by stacking a metal layer (4 nm)/silver layer (16 nm)/oxygen-deficient metal oxide layer (4 nm)/metal oxide layer (30 nm) in this order. Thus, an infrared reflective film 1 was obtained.

In the infrared reflective films 2 to 6, the thicknesses of the metal oxide layer, the oxygen-deficient metal oxide layer, and the silver layer were changed during sputtering from the manufacturing method of the infrared reflective film 1, and the thicknesses shown in Tables 1 and 2 below were used. Infrared reflective films 2 to 6 were obtained by adjusting the reflectances at the first and second maximum reflection wavelengths and the first and second maximum reflection wavelengths shown in Tables 1 and 2 below.

Nano90S (3M, multilayer resin film, "Multilayer Nano 90S" manufactured by Sumitomo 3M)

The following laminated glass members were prepared.

(Laminated glass member)

Green glass (heat-absorbing plate glass, thickness 2mm)

Clear glass (thickness 2.5mm)

(Example 1)

Preparation of the first resin layer:

The following ingredients were blended and thoroughly kneaded with a mixing roll to obtain a composition for forming the first resin layer.

100 parts by weight of polyvinyl acetal resin (PVB, average polymerization degree 1700, hydroxyl group content 30.5 mol%, acetylation degree 1 mol%, acetalization degree 68.5 mol%)

40 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO)

Anthraquinone compound (Component X-1, "Sumiplast Violet RR" manufactured by Sumika Chemtex Co., Ltd.) in an amount of 0.77% by weight in the resulting resin layer

Tinuvin 326 (2-(2'-hydroxy-3'-t-butyl-5-methylphenyl)-5-chlorobenzotriazole in an amount of 0.2% by weight in the resulting resin layer, BASF "Tinuvin 326" )

BHT (2,6-di-t-butyl-p-cresol) in an amount of 0.2% by weight in the resulting resin layer

The obtained composition for forming the first resin layer was extruded by an extruder to obtain the first resin layer. The first resin layer was rectangular and had a thickness of 380 μm.

Preparation of the second resin layer:

The following components were blended and sufficiently kneaded with a mixing roll to obtain a composition for forming the second resin layer.

100 parts by weight of polyvinyl acetal resin (PVB, average polymerization degree 1700, hydroxyl group content 30.5 mol%, acetylation degree 1 mol%, acetalization degree 68.5 mol%)

40 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO)

Tinuvin 326 (2-(2'-hydroxy-3'-t-butyl-5-methylphenyl)-5-chlorobenzotriazole in an amount of 0.2% by weight in the resulting resin layer, "Tinuvin 326" manufactured by BASF) )

BHT (2,6-di-t-butyl-p-cresol) in an amount of 0.2% by weight in the resulting resin layer

The obtained composition for forming the second resin layer was extruded by an extruder to obtain the second resin layer. The second resin layer was rectangular and had a thickness of 380 μm.

Preparation of infrared reflective layer and first and second laminated glass members:

An infrared reflective film 1 was prepared as an infrared reflective layer.

As the first laminated glass member, green glass (heat absorbing plate glass, thickness 2 mm) was prepared.

A clear glass (thickness: 2.5 mm) was prepared as the second laminated glass member.

Fabrication of laminated glass:

A first laminated glass member, a first resin layer, an infrared reflective layer, a second resin layer, and a second laminated glass member were laminated in this order to obtain laminated glass. The wedge angle of the first laminated body of the first laminated glass member and the first resin layer was the same as the wedge angle of the first resin layer.

(Examples 2-6 and Comparative Examples 1-6)

A laminated glass was obtained in the same manner as in Example 1, except that the structure of the intermediate film was changed as shown in Tables 1 and 2 below.

Comparative Examples 1 to 3 did not use an infrared reflective layer. In Examples 2 to 6 and Comparative Examples 1 to 6, the same ultraviolet shielding agent and antioxidant as in Example 1 were added to the first and second resin layers, and the same ultraviolet shielding agent and antioxidant as in Example 1 were added to the resin layer. It was blended in the blending amount. The colorant was blended in the amount shown in Tables 1 and 2 below in 100% by weight of the resulting resin layer.

(evaluation)

(1) Light resistance test

The obtained laminated glass was held for 3000 hours with a xenon weather meter NX25 (manufactured by Suga Test Instruments Co., Ltd.), and then evaluated according to the following criteria. A lower color difference ΔE is preferable.

[Criteria for light resistance test]

○: Color difference ΔE before and after the light resistance test is lower than 4

×: Color difference ΔE before and after light resistance test is 4 or more

(2) Heat resistance test

The obtained laminated glass was kept in a constant temperature bath at 100° C. for 12 weeks and evaluated according to the following criteria. A lower color difference ΔE is preferable.

[Criteria for heat resistance test]

○: Color difference ΔE before and after heat resistance test is less than 1

×: Color difference ΔE before and after heat resistance test is 1 or more

Details and results are shown in Tables 1 and 2 below. In addition, description of an ultraviolet shielding agent and an antioxidant is omitted in the table.

1... Infrared reflective layer

1a... First surface

1b... second surface

2... First resin layer

2a... Outer surface

3... Second resin layer

3a... Outer surface

11, 11A... Intermediate film

11a... First surface

11b... second surface

21... First laminated glass member

22... Second laminated glass member

31, 31A... Laminated glass

Claims (9)

A first laminated glass member, a second laminated glass member, and an interlayer film for laminated glass,
The interlayer film for laminated glass has an infrared reflective layer, a first resin layer containing a thermoplastic resin , and a second resin layer containing a thermoplastic resin ,
The first resin layer is arranged on the first surface side of the infrared reflective layer,
The second resin layer is arranged on the second surface side opposite to the first surface of the infrared reflective layer,
The first laminated glass member is arranged outside the first resin layer,
The second laminated glass member is arranged outside the second resin layer,
The infrared reflective layer has a first maximum reflection wavelength at a wavelength of 350 nm to 450 nm and a second maximum reflection wavelength at a wavelength of 800 nm or more, and the reflectance at the first maximum reflection wavelength and the second maximum Each reflectance at the reflected wavelength is 15% or more,
The first resin layer contains a coloring agent,
the second resin layer does not contain a coloring agent,
The first laminated glass member is a laminated glass member positioned on the inner space side,
A laminated glass, wherein the second laminated glass member is a laminated glass member positioned on the outside space side . 2. The laminated glass of claim 1, wherein the infrared reflective layer comprises a metal sputtered layer. 3. The laminated glass according to claim 1, wherein said coloring agent in said first resin layer is a perylene compound, a phthalocyanine compound, a naphthalocyanine compound or an anthracyanine compound . The laminated glass according to any one of claims 1 to 3, wherein the first resin layer contains heat shielding particles. The laminated glass according to any one of claims 1 to 4, wherein said thermoplastic resin in said first resin layer is a polyvinyl acetal resin. The laminated glass according to any one of claims 1 to 5, wherein the first resin layer contains a plasticizer. The laminated glass according to any one of claims 1 to 6 , wherein said thermoplastic resin in said second resin layer is a polyvinyl acetal resin . The laminated glass according to any one of claims 1 to 7 , wherein the second resin layer contains a plasticizer . In a building or a vehicle, the second laminated glass member is positioned on the exterior space side in an opening between an exterior space and an interior space into which heat rays are incident from the exterior space. The laminated glass according to any one of claims 1 to 8, wherein one laminated glass member is attached so as to be positioned on the inner space side.

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